Vat dyeing compositions, including a mixture of cobalt phthalocyanine dyes



Patented Oct. 7, 1952 VAT DYEING COMPOSITIONS, INCLUDING A MIXTURE OF COBALT PHTHALOCYANINE DYES Fritz Baumann,

Leverkusen-Bayerwerk, and

Berthold Bienert, Leverkusen-Wiesdorf, Germany, assignors to Farbenfabriken Bayer, Leverkusen, Germany 1 No Drawing. Application Marchll, 1949, Serial No. 81,025. In GermanyOctober 29, 1948 1- The present invention relates to new compositions of matter which are useful for dyeing textile fibers from the vat.

The phthalocyanines which are distinguished by clear shadesand excellent fastness properties have been used as yet only for pigmenting, as

substantive dyestuffs and as dyestuffs for lakemaking. In British Patentv No. 322,169' some indications are given of phthalocyanines being suitable for the dyeing from the vat. These indications refer both to unsulphonated and sulphonated products, specific mention being made of the copper, nickel and iron complex. In reality, unsulphonated copper and nickel phthalocyanines have no vatting properties. Sulphonation products thereof are capable of being vatted but do not dye the fiber from the vat to any material extent. Unsulphonated. as well as sulphonated iron phthalocyanines are capable of use as vat dyes, also exhibit some affinity to the fiber, but yield unsatisfactory shades.

We have now found that cobalt phthalocyanines are far superior to all otherphthalocyanines as far as vatting properties are concerned. Contrary to the unsubstituted copper and nickel complex the unsubstituted cobalt phthalocyanine is capable of use as a vat dye and, on dyeing from the vat, yields essentially clearer shades than the iron complex. Furthermore, in contrast to all other phthalocyanines as far as theseare vattable at all, the vatted cobalt phthalocyanine is distinguished by excellent stability on dyeing,

from the hot vat. The property of vatting and yielding clear valuable dyeings on textiles from the vat is not restricted to the unsubstituted cobalt phthalocyanine. According to our present invention, the above properties to a larger extent are met with those substitution products of cobalt phthalocyanine the hydrophilic property of which has been increased by substitution. For accomplishing this efiect, substituents of different kind may be used, for instance, sulphonic acid groups, sulphonamide groups (the nitrogen of which may be monoor disubstituted by alkyl-, arylor aralkyl radicals), sulphinic acid groups, carboxylic, acid groups, carboxylic amide groups, cyano groups, hydroxy groups, alkoxy groups, --SH groups, -S.alkyl groups, nitro groups, amino groups, or acylamino groups. These groups may be introduced. into the cobalt phthalocyanine as usual, i. e. either subsequent to complex formation or in the course of preparing the complex by starting from phthalic acids, phthalonitriles etc. containing such substituents. e. g. l-sulphophthalic acid, i-methoxyphthalic 2 Claims. (01. 8--28) acid etc. As. a matter of fact, besides such substituents as increase the hydrophilic property, the cobalt phthalocyanines may also contain substituents which exert the contrary eiiect, provided however, that there are sufficient hydrophilic substituents in order to accomplish at least a higher hydrophilic character than in the case of cobalt phthalocyanine. All these substitution products have generally better vatting properties than the unsubstituted cobalt phthalocyanine itself. This is true with the reservation that the number of hydrophilic groups must not be so high as to render the products easily soluble in water as otherwise the aifinity to the fiber of the vatted product will be impaired. For this reason, it is advisable to substitute the dyestuffs with only a small number of strong hydrophilic groups, such as SOsH-groups or COOH-groups.

Our present invention also comprises the application of cobalt phthalocyanines with increased hydrophilic properties in admixture with the unsubstituted cobalt phthalocyanine or with cobalt phthalocyanines containing other substituents. We have found that even small amounts of hydrophilic cobalt phthalocyanines will do to convert larger amounts of non-hydrophilic phthalocyanines with poor vatting properties into a state in which they exhibit excellent vatting properties. Such mixtures may be obtained in a simple manner, for instance, by starting on. cobalt phthalocyanine synthesis from a preponderant amount of phthalic acid in admixture with a small amount of hydrophilic substituted phthalic acids. Another possibility of preparing such dyestuff mixtures consists in subsequently introducing small amounts of hydrophilic substituents into the phthalocyanine molecule. I

Among the various combinations of cobalt phthalocyanines with hydrophilic groups and such without hydrophilic groups as described in the foregoing paragraph, mixtures of the unsubstituted cobalt phthalocyanine with low sulphonated cobalt phthalocyanine are of the greatest importance. On the preparation of such cobalt phthalocyanine sulphonic acids care must be taken that, in the first line, monosulphonic acids will be obtained. Such combinations may be prepared either by cautiously sulphonating cobalt phthalocyanine or by starting on phthalocyanine synthesis from a mixture of smaller amounts of sulphophthalic acid with larger amounts of phthalic acid. Combinations thus obtained may be blended with unsulphonated cobalt phthalocyanine so as to exhibit the desired degree of solubility. The best results are obtained from combinations of cobalt phthalocyanine sulphonic acids and unsulphonated cobalt phthalocyanine in which the cobalt phthalocyanine sulphonic acids are present in an amount of -40% by weight (calculated as monosulphonic acid).

In these mixtures, sulphonic acid groups can be replaced with a similar effect by alkylsulfonamide groups.

Cobalt phthalocyanine and the various hydrophilic substitution products mentioned above as well as the combinations described in the fore going will dye cellulose fibers accordingto the methods usually applied to vat dyestuffs. In general, the best aflinity is reached when dyeing from the hot vat. Many cobalt phthalocyanines are capable of being vatted even in a weakly alkaline medium, for instance, in the presence of ammonia and, therefore, may also be used for dyeing animal fibers from the vat.

The following examples illustrate the invention without restricting it thereto, the parts and percentages being by weight if not otherwise stated.

Examples A-C describe various dyeing processes whereas Examples 1-22 refer to the preparation of various dyestuffs to be used for such dyeing processes.

Example A describes the vat dyeing with cobalt phthalocyanine vat dyestuffs on cotton:

100 parts by volume of a cobalt phthalocyanine paste (corresponding to 1 part of the 100% dyestufl) are added to 650 parts by volume of water and 7 parts by volume of concentrated caustic soda solution (38 B.) at 50 C. 40 parts by volume of sodium hydrosulphite solution (1:10 dissolved in water) are caused to react with the above mixture for 15 minutes at 50 C. 200 parts by volume, of Glaubers salt solution (1:10 dissolved in water) are then added and 50 parts of cotton are dyed in the usual manner at 50 C. for one hour. After lifting the cotton is squeezed oil and hanged in the air for 10 minutes; it is rinsed in cold water, the dyeing is treated with dilute sulphuric acid (2 parts by volume per 1000 parts by volume of water) and it is rinsed once more with water. The dyeing is then washed at the boil with Marseilles soap (2 parts per 1000 parts by volume of water), rinsed and dried. Full, blue to green, olive-green or grey shades are obtained.

Example B.-3 parts by volume of caustic soda solution of 38 B., parts by volume of a paste of a cobalt phthalocyanine 1:100 (corresponding to 0.2 part of the 100% dyestuff) and 8 parts by volume of a sodium hydrosulphite solution (1 part dissolved per 10 parts by volume of water) are added to 170 parts by volume of water of 60 C. After 15 minutes 10 parts of cotton are dyed therein in the usual manner and, after hanging in the air, it is proceeded as described in Example A. That process can be modified by substituting 3 parts by volume of caustic soda solution by 4.5 parts by volume of caustic soda solution or by adding 40 parts by volume of Glaubers salt solution (1 part per 10 parts of water).

Example C describes the process of a vat dyeing on wool:

0.2 part of a cobalt phthalocyanine easily capable of being vatted (for instance the dyestuff obtained according to Example 22) is vatted by means of 2 parts by volume of concentrated ammonia (25%) and 0.75 part of sodium hydrosulphite in 120 parts by volume of water at about 75 C. The vat is then filled up to 500 parts by volume by adding water. 10 parts of wool are dyed in this liquor in the usual manner at 51-52 C. for 1 hour. After lifting and wringing out the wool is hanged in the air for 20 minutes. rinsed with water and treated with dilute acetic acid (5 parts by volume of glacial acetic acid per 1000 parts by volume of water), rinsed and dried. Dyeings of good fastness properties are obtained.

Example 1 describes the preparation of a mixture easily capable of being vatted of a cobalt phthalocyanine sulphonic acid with cobalt phthalocyanine:

1.6 parts of cobalt phthalocyanine are gradually added while stirring into 20 parts of 10% fuming sulphuric acid at room temperature. The green solution thus obtained is heated for about 4 hours at 35-38 C. until a sample which has been washed neutral with water begins to dissolve on heating with pyridine water. This degree of sulphonation is reached when about 2.7-2.9% of sulphur have entered the molecule of the cobalt phthalocyanine. When this point is reached sulphonation is stopped and the solution is diluted below 40 C. with 36 parts of sulphuric acid of 66" B. When the solution 7 shows only a small amount of free $03, 2.4 parts of cobalt phthalor cyanine are added below 25 C. and, as soon as dissolution is completed, the whole is stirred into about 400 parts of ice water. The precipitated dyestuff is filtered off and washed with hot water. The product dyes cotton from olive colored vat full, clear greenish-blue shades which are distinguished by excellent fastness to light.

A vat dyestufl of equal dyeing properties is obtained by heating 20 parts of cobalt phthalocyanine in parts of 10% fuming sulphuric acid at 45-48 C. for 2-3 hours until a sample which has been washed neutral with water can easily be vatted with sodium hydrosulphite and dilute caustic soda solution. If this is not the case, further 10-20 parts of 20% fuming sulphuric acid have to be added. The dyestuff is precipitated by stirring the solution into ice water and washing the precipitate with hot water.

Example 2 describes the preparation of a cobalt phthalocyanine with good vatting properties from phthalic acid anhydride and sodium 4- sulphophthalate A mixture of 10.36 parts of phthalic acid anhydride 2.86 parts of sodium 4-sulphophthalate 3.74 parts of cobalt sulphate (83%) 2.34 parts of ammonium chloride 29.00 part of urea and 0.34 part of ammonium molybdate moved from the dyestuif. After drying about 10.8

parts of a cobalt phthalocyanine are obtained which, after redissolving from sulphuric acid monohydrate, dyes cotton from olive colored ,vat full, clear, blue shades of excellent fastness .to light.

Example 3.A mixture of- 4.44 parts of phthalic acid anhydride 2.26 parts of phthalimide-4-sulphonamide 1.55 parts of cobalt sulphate (83%) 1.18 parts of ammonium chloride 14.5 parts of urea and 0.18 part of ammonium molybdate aeiaiae isgra'dually added to. 14.5. partsoivolume oi. trichlorobenzene and the melt is further heated at 180 C; ior 5-6 hours. On processing as: described in Example 2 a cobalt. phthalocyanine with good vatting properties is obtained which dyes cotton full, very clear, blue shade of excellent fastness to light. The color of the. vat. is olive.

Example 4.- -A mixture 015-- 11.1 parts of phthalic acid anhydride 6.1 parts of phthalimide e-sulphomethylamide 4.7 parts of cobalt sulphate (83%) 2.5 parts of ammonium chloride 24.0 parts of urea and 0.4 part of ammonium. molybdat is gradually added to 30 parts by volume of trichlorobenzene of 180 C. and the melt is further heated at 180 C. for about 6' hours. On proceeding as described in Example 2 a cobalt phthalocyanine is obtained which after pasting from a mixture of sulphuric acid monohydrate and chlorosulphonic acid (5:1) dyes cotton from yellow-olive colored vat full, blue shades of good fastness to water and excellent fastness to light.

Example 5 .--A mixture of-- 8.88 parts of phthalic acid anhydride 5.08 parts of phthalic acid-4-sulphodimethy amide 3.74 parts of cobaltsulphate (83%) 2.34 parts of ammonium chloride 29.00 parts of urea and 0.34 part of ammonium molybdate is gradually added to 20 parts by volume of nitrobenzene of 180 C. and the melt is further heated at 180 C. for about 6 hours.

On proceeding as described in Example 2 a cobalt phthalocyanine is obtained which, after pasting from a mixture of sulphuric acid monohydrate and chlorosulphonic acid (.5 1), dyes cot-'- ton .from yellow-olive colored vat full, greenishblue shades of excellent fastness. to light and good fastness to water.

Example 6 describes the preparation. of a dyestuff with good vatting properties from cobalt phthalocyanine and phosgenei parts of cobalt phthalocyanine are added at l- -'C. to 100 parts of amixture of aluminum chloride and sodium chloride (7:1). Phosgene is introduced at -155 C. As soonas a sample of the mix is capable of being readily vatted but not yet soluble in dilute caustic soda solution or only slightly soluble, the reaction is stopped and the dyestufi is isolated as usual. either directly be used for vat dyeing or, after drying and pasting from sulphuric. acid, in the presence of'the same amount of cobalt phthalocyanine. In the latter case, somewhat redder and fuller shades are obtained.

Example 7 .A mixture ofis gradually added to 14 parts by volume of nitro- I benzene of C. The melt is further heated at 180 C. for 6 hours while stirring and it is proceeded as described in Example 2. The dyestuil thus obtained dyes cotton from olive-colored vat full, clear, blue shades of good f astness to water and excellent fastness to light.

The dyestuil may Example 8 describes the. preparation. of a, dyestuff with good vatting properties from cobalt phthalocyanine and phthalic acid anhydride:.

A mixture ofi 1 part of cobalt phthalocyanine. 2 parts of water-free aluminum. chloride and 10 parts of. phthalic acid anhydride 8.5 parts of 4-bromophthalic acid anhydride 3.05 parts of phthalimide-4-s,ulphomethylamide 2.35partsof cobalt sulphate (83%) 1.25 parts of ammonium chloride 12.00 parts of urea. and

0.2 part of ammonium molybdate is gradually added while stirring to 15 parts by volume of trichlorobenzene of 180 C. and the melt is further heated at 180 C. for about 6 hours.

On proceedin as described in Example 2, a cobalt phthalocyanine is obtained which after pasting dyes cotton from olive-colored vat full. greenish shades.

Example 10.If phthalimide-4-sulphomethylamide (of. Example 3) is replacedby an equiva lent amount of 4-nitrophthalic acid there is obtained a. dyestufi' which dyes. cotton. from the vat full, greenish-blue shades of good fastness to water and very good fastness to light.

Example 11.-A mixture of 16.9 parts of 4-nitrophthalic acid 3.1 parts of cobalt sulphate (83%) 2.35 parts of ammonium chloride 29.0 parts of urea and 0.35 part of ammonium molybdate is gradually addedv while stirring to 29 parts by volume of trichlorobenzene at 180 C. and the melt is further heated at 180 C. for 6-7 hours.

On proceeding as described in Example 2 there is obtained 4.4.4".4"'-tetranitrocobalt phthalooyanine in a good yield which dyes cotton from yellow-colored vat very full, olive-green shades, the nitro groupsbeing converted thereby into amino groups. The dyeings which are distinguished by very good fastness to light can be 'diazotized' on the fiber and can be reacted in the usual way with coupling components, very full, olive-green to dark green dyeings of very good fastness to light and excellent fastness to water being obtained thereby.

Example 12.-A. mixture of 6.00 parts of 4-acetylamino phthalic acid 1.26 parts of cobalt sulphate (83%) 0.78 part of ammonium chloride 9.8 parts of urea and 0.11 part of ammonium molybdate is. gradually added while. stirring to 18 parts by volume of nitrobenzene at 180 C. and the melt is further heated while. stirring at 180 C. for 6- hours. On proceeding as described in Example 2 a cobalt phthalocyanine is obtained which, after pasting. dyes cotton from olive-green colored vat bluish-green shades of excellent fastness: to light.

7v Example 13.A mixture of- 7.36 parts of 4-methoxyphthalic acid 1.87 parts of cobalt sulphate (83%) 1.17 parts of ammonium chloride 0.17 part of ammonium molybdate and 14.5 parts of urea is gradually added while stirring to 15 parts by volume of trichlorobenzene at 180 C. Thereupon, it is proceeded as described in Example 2.

4.4 .4 .4 -tetramethoxy cobalt phthalocyanine thus obtained dyes cotton from yellow-olive colored vat full, clear turquoise blue shades of excellent fastness to light and very good fastness to water.

Example 14 describes the preparation of a dyestuif with good vatting properties from cobalt phthalocyanine and sulphur chloride:

Starting at 50 C., 4 parts of cobalt phthalocyanine are added to a mixture of 12 parts of water-free aluminum chloride and 24 parts of sulphur chloride, the temperature being raised thereby to 60 C. Temperature is kept at 60 C. until a sample treated with sodium hydrosulphite and dilute caustic soda solution yields a clear, olive-brown vat, this stage being achieved after about 3 hours. The greenish-blue vat dyestuff can be separated, for instance, by introducing the reaction mixture into dilute hydrochloric acid, sucking off and afterwashing with Water.

For further purification the paste of the crude dyestufi is extracted with sodium sulphide solution a small amount of a greenish-blue dyestuff being dissolved thereby besides sulphur. The insoluble blue dyestuff is filtered off, washed with water and dried, and can directly be used for dyeing from the 'vat.

Example 15.-A mixture of-- 13.32 parts of phthalic acid anhydride 6.33 parts of 4-nitrophthalic acid 5.6 parts of cobalt sulphate (83%) 3.51 parts of ammonium chloride 43.5 parts of urea and 0.51 part of ammonium molybdate is added while stirring to 44 parts by volume of nitrobenzene at 180 C. and the whole is further heated while stirring at 180 C. for 5-6 hours. On proceeding as described in Example 2, 4- mononitro-cobalt phthalocyanine is obtained which, in the usual way, is converted on reduction with sodium sulphid into 4-mono-amino cobalt phthalocyanine and, at last, into 4-mono-mercapto-cobalt phthalocyanine by diazotizing and treating the diazonium compound with potassium thiocyanate and saponifying. 4-monomercapto cobalt phthalocyanine dyes cotton from yellowolive colored vat full, green to blue shades of excellent fastness to light.

Example 16.On processing according to Example 15 starting, however, from 8.88 parts of phthalic acid anhydride and 12.66 parts of 4- nitrophthalic acid, 4.4-dimercapto cobalt phthalocyanine is obtained which dyes cotton from the vat full, blue to green shades.

Example 17.On processing according to Example 15 starting, however, from 4.44 parts of phthalic acid anhydride and 18.99 parts of 4'- nitrophthalic acid, 4.4.4-trimercapto cobalt phthalocyanine is obtained which dyes cotton from yellow-olive colored vat bright, full, bluishgreen shades of excellent fastness to light.

Example 18.On'processing according to Example 15 leaving out, however, phthalic acid anhydride and using 25.32 parts of 4-nitrophthalic acid, 4.4 .4' .4 -tetranitro-cobalt phthalocyanine is obtained. 4.4'.4".4"' tetramercapto cobalt phthalocyanine obtainable therefrom dyes cotton from olive colored vat greyish-green shades which, on aftertreating with bichromate in acetic acid, turn fully, grey, the fastness to water-being very good.

Example 19.-A mixture of- 4.84 parts of diphenyl-3.4-dicarboxylic acid 4.80 parts of phthalimide-4-sulphomethylamide 1.84 parts of cobalt sulphate (83%) 0.98 part of ammonium chloride 9.44 parts of urea and 0.16 part of ammonium molybdate is introduced while stirring into 12 parts by volume of trichlorobenzene at C. and it is proceeded as described in Example 2. The cobalt dyestuif thus obtained dyes, after pasting from ethyl sulphuric acid, cotton from yellow-olive colored vat full, greenish-blue shades.

Example 20.A mixture of- 3.68 parts of 4-methoxyphthalic acid 4.84 parts of diphenyl-3.4-dicarboxylic acid 1.87 parts of cobalt sulphate (83%) 1.17 parts of ammonium chloride 14.5 parts of urea and 0.17 part of ammonium molybdate is introduced while stirring into 15 parts by volume of trichlorobenzene at 180 C. and the melt is further heated while stirring at 180 C. for 5-6 hours. On proceeding as described in Example 2 a cobalt phthalocyanine is obtained which, after pasting from ethyl sulphuric acid, dyes cotton from yellow-olive colored vat clear, full, greenish-blue shades of good fastness to water and excellent fastness to light.

Example 21 .-A mixture of- 49.0 parts of benzophenone 4.53 parts of anthraquinone-Z"-carboyl-4'-amino 3.4 dicyanodiphenyl (prepared from 4'- amino 3.4 dicyanodiphenyl and anthraquinone-2-carboxylic acid chloride) 3.84 parts of phthalodinitrile and 1.62 parts of dehydrated cobalt chloride 22 parts of urea 18 parts of the condensation product of 4-aminophthalimide and betaindichloride 2.8 parts of cobalt sulphate (83%) 1.8 parts of ammonium chloride 0.25 part of ammonium molybdate and 2.2 parts of benzamide is introduced at 180 C. into a stirring vessel and the melt is stirred at 180-185 C. for 2-3 hours. The melt being still in a warm condition is diluted with 440 parts by volume of water, acidified with hydrochloric acid and the dyestuff thus obtained is salted out by adding 880 parts by volume of common salt solution. The dyestuff can be purified by dissolving once more in dilute hydro- 9 10 chloric acid and saiting out with common salt REFERENCES man and is soluble in dilute mineral acids with a The following reference-'5, are f. record n the fi 'f f file of this patent:

e c a m:

1. A vat dyeing composition comprising a 5 UNITED STATES E cobalt phthalocyanine free from hydrophilic Number Name Date groups, a cobalt phthalocyanine monosulphonic 2,133,340 Bienert Oct. 18, 1938 acid, sodium hydrosulphite, water, and caustic FOREIGN PATENTS soda.

2. A vat dyeing composition comprising a mix- 10 Number Country Date ture of 60-85% of a cobalt phthalocyanine free 322 169 Great Britain Nov. 18, 1929 from hydrophilic groups and of 15-40% of cobalt phthalocyanine monosulphonic acid, sodium hydrosulphite. water. and caustic soda.

FRITZ BAUMANN. 15 BERTHOLD BIENERT. 

1. A VAT DYEING COMPOSITION COMPRISING A COBALT PHTHALOCYANINE FREE FROM HYDROPHILIC GROUPS, A COBALT PHTHALOCYANINE MONOSULPHONIC ACID, SODIUM HYDROSULPHITE, WATER, AND CAUSTIC SODA. 